Process of reforming metal material

ABSTRACT

The casting characteristics of ferrous and nonferrous molten metals as well as the physical properties of ingots and other castings formed therefrom can be considerably improved by processing the melt with appropriate reducing-gas forming hydrocarbon materials such as petroleum oil or grease at any casting stage or stages before it finally solidifies in a mold. The reducing-gas forming materials are placed together with suitable carbon or carbonaceous materials in direct reacting contact with the metal in the ladle or mold or while it is being tapped into the ladle.

nited States atent 1 Otani [451 Jan. 28, 1975 PROCESS OF REFORMINGMETAL MATERIAL [63] Continuation-impart of Ser. No. 697,568, Jan. 11,

1968, abandoned.

[52] US. Cl. 75/96, 75/53, 75/94 [51] lint. Cl C22b 9/00 [58] Field of Search 75/96, 53, 94; 164/55, 164/72, 74, 33; 44/7 [56] References Cited UNITED STATES PATENTS 2,245,651 6/1941 Craig 164/72 2,430,655 11/1947 Wallace 3,052,936 9/1962 Hamilton 75/53 3,322,518 5/1967 Hammerton 44/7 3,376,914 4/1968 Emm0tt..... 3,567,432 3/1971 Wardell Primary Examiner-C. Lovell Assistant ExaminerPeter D. Rosenberg Attorney, Agent, or FirmOldham & Oldham Co.

[57] ABSTRACT The casting characteristics of ferrous and nonferrous molten metals as well as the physical properties of ingots and other castings formed therefrom can be considerably improved by processing the melt with appropriate reducing-gas forming hydrocarbon materials such as petroleum oil or grease at any casting stage or stages before it finally solidifies in a mold. The reducing-gas forming materials are placed together with suitable carbon or carbonaceous materials in direct reacting contact with the metal in the ladle or mold or while it is being tapped into the ladle.

18 Claims, No Drawings PROCESS OF REFORMING METAL MATERIAL This is a continuation-in-part of my prior U.S. application Ser. No. 697,568, filed Jan. 11, 1968, and now abandoned.

The present invention relates generally to the making ofingots or other castings of ferrous and nonferrous metals and more particularly to the handling, or processing of molten metal in the casting process.

As is well known, molten metal formed in a furnace, a converter or the like device does not at all times exhibit satisfactory casting characteristics and there has been an increasing demand for ingots and other metal castings having improved physical properties.

Under this situation, the present invention has for its general object to provide a novel process for reforming ferrous and nonferrous metal casting materials in their molten state before they are finally cast in molds. The term reforming as used herein means to improve the casting characteristics of the molten metal and hence, the physical properties of ingots or other castings obtainable from the melt.

Molten metal formed in a furnace or the like is usually teemed or tapped therefrom into a ladle for casting in molds and, being thus exposed to the atmospheric air, forms a layer of oxides on top of the molten mass in the ladle or molds. This apparently involves the danger of undesirably introducing some oxygen into the molten mass and thus degenerating its quality. In order to preclude formation of such oxide layer while at the same time restraining the temperature drop of the molten metal, it has usually been a practice to spread an appropriate organic carbonaceous cover material, or materials, such as straw-mats, chaff, straw and floatboards, over the surface of molten metal in the ladle and thus to form a generally coarse and dry heatinsulating layer on the melt.

The casting of molten metal in molds lies in substantially the same situation as described above in connection with the melt tapping and it is also conventional to form such heat-insulating layer on the surface of molten metal in casting molds.

One specific object of the present invention is to enhance the advantageous effects of such organic cover material, which is laid on a molten metal mass to physically shield and thermally insulate it from atmospheric air and thus to enable economic production of high quality metal castings which include only minimum amounts of impurities and particularly of gases.

Another object of the invention is to use combinations of hydrocarbons and carbon or carbonaceous materials in the treatment of molten metals.

Other objects of the invention are to provide improved quality castings of both ferrous and nonferrous metals; to provide ingots free from blowholes; to provide efficiently machineable steel castings; to provide improved physical characteristics in alloy metal castings; and to use commercially available materials in novel quantities and manners in reforming molten metals to obtain improved products.

To attain this object, the present invention proposes to add some animal, vegetable or petroleum oil, grease or the like combustible hydrocarbon material to the dry cover material conventionally used on top of the molten metal in the ladle or casting molds. Satisfactory results can be obtained, for example, by spraying an appropriate liquid hydrocarbon material onto the layer of cover material previously spread over the molten metal surface or alternatively by forming a desired shielding layer on the molten metal surface which includes orcover layer, to which the liquid hydrocarbon is added,

forming a huge shielding screen of flames, which spreads over the surface ofthe molten mass and acts to completely shield or separate the molten metal surface from the cold atmospheric air and thus to effectively keep the metal from cooling down.

According to another aspect of the present invention, substantially the same satisfactory results as those described above can be obtained by placing reducing-gas forming material, such as kerosene or other petroleum hydrocarbon or other hydrocarbons such as animal oil, vegetable oil, petroleum oil, grease, fat, benzene, or wax, in the bottom of a ladle or a casting mold together with carbon material such as breeze or graphite. The hydrocarbon material may conveniently be sprayed or sprinkled over the carbon previously laid in the ladle or mold bottom to form a desired mixture therein.

In any case, the solid carbon material used in the ladle or mold bottom in combination with hydrocarbon material effectively prevents the latter from rising afloat through the mass of molten metal in the ladle and thus enables the hydrocarbon to fully act upon the oxygen gas contained in the melt, evolving carbon monoxide, hydrogen and other reducing gases in large quantities. The evolution of these reducing gases serves satisfactorily to deoxidize the molten metal and facilitates production of high quality ingots or other metal castings.

It is to be appreciated that the use of combustible reducing-gas forming hydrocarbon materials according to the present invention is effective not only to fully preclude the formation of an oxide film or layer on the surface of molten metal under the action of atmospheric gases and the induction of oxygen or other gases into the molten metal but is also effective to keep it at elevated temperature allowing the melt to exhibit and maintain an increased fluidity. In this manner, the molten metal can be held longer in a state permitting the gases included therein to be freely released into the atmosphere and the vigorous release of gases enables production of fully deoxidized and otherwise improved high quality castings from such molten metal.

For example, in the case of pig iron, it has been found that its casting characteristics can be improved by the process of the present invention to such an extent as to stand comparison with so-called charcoal pig; the molten iron after the processing can remain in its molten state longer than before, exhibiting a satisfactorily high fluidity. In applications likerthis, it will be understood that appropriate refining agents may be added to the gas-forming material if desired to deal with the Si and other impurity contents of the iron or other metal casting material.

In practicing the process of the present invention, reducing-gas forming hydrocarbon material may be placed in the ladle or mold bottom as a mixture with carbon material such as breeze or graphite packed in small open-ended tubes instead of employing a direct mixture of the two materials or may be incessantly thrown into the ladle or into the chute upstream thereof while the molten metal is being transferred therethrough into the ladle. If desired, an appropriate hydrocarbon and carbon mixture may be held in a suitable barrel or cage for immersion into the mass of molten metal received in the ladle or casting mold.

In either case, the petroleum or other combustible hydrocarbon material placed in direct contact with the molten metal, for example, in the ladle, readily burns forming deoxidizing flames to deprive the molten metal of any excess of oxygen and thus a mass of reformed molten metal, which is free from oxide impurities, is provided in the ladle. When it is subsequently cast in molds, all the gases undesirably included in the molten metal mass are released therefrom before it completely solidifies and high quality ingots having no blowholes are formed.

Particularly in steelmaking processes, use of the method of the present invention enables production of killed steel ingots which involve much less blowholes and are more tenaceous than those conventionally obtainable.

In the past, it has never been attempted in metal casting processes to put hydrocarbon oil such as heavy oil or kerosene in the mass of molten metal with the intention of reforming the latter not only because it seems to involve the danger of explosion as pointed out hereinbefore but also because it may undesirably introduce hydrogen into the molten metal. It has been found, however, that the carbon and hydrogen freshly contained in the melt as the result of decomposition of the hydrocarbon oil are active deoxidizing gases and, reacting with the molten metal, readily combine with oxygen to form carbon monoxide, H and other gases and thus help developing high heatjust like the gases evolving in the iron or steel melt including charcoal pig. Also, in the case of cast iron, a deep chilling effect can be obtained just as with the case of castings including charcoal pig.

The use of carbon or carbonaceous material in combination with petroleum or other combustible hydrocarbon material provides an additional practical advantage that it substantially extends the burning time of the hydrocarbon added to the molten metal and enables the hydrocarbon material fully to serve the intended purpose in cooperation with the carbon or carbonaceous material.

The carbon or carbonaceous material usable in the inventive process should preferably be easy to impregnate or saturate with oil and can be selected from carbon materials including charcoal, coke, electrode ships, breeze and graphite powder or from organic materials including straw, straw-mats, chaff, pasteboard and dry fiber. Without such carbon or carbonaceous material, oils cannot continue to burn for any long period and in this respect less inflammable hydrocarbons including grease and wax are preferred and when used with appropriate carbon or carbonaceous material have their burning time further extended.

For some metal castings, it is undesirable to allow any part of the added carbon to remain in the metal and it is recommended to use dry chaff or the like organic material which readily burns to gasify. The amount of such organic material can be reduced without the danger of impairing its effectiveness when it is used together with grease or wax or oil of higher viscosity.

In general, metal castings obtained according to the present invention have a uniform structure involving only limited lamination or segregation and it has been confirmed by electron microscopic examination that impurities are scarcely found in the boundary regions between crystal grains but tend to be finely dispersed in the whole structure of the castings. Moreover, castings obtained from the molten metal reformed by the inventive process exhibit a specific heat lower than that of castings obtainable from ordinary molten metal and a more or less higher heat conductivity, as will be described hereinafter.

INVENTIVE CONCEPT This invention relates to a process for reforming metal material namely ferrous and nonferrous metal casting materials in their molten state before they are finally cast in molds, by placing about 0.9 10 Kg of hydrocarbon material per 1000 Kg. of molten metal together with carbon or carbonaceous material at arate ranging from about one part by weight of hydrocarbon material to about 3 5 parts by weight of carbon material in direct contact with the molten metal thereby to avoid blowholes in the ingot, and remove oxygen gas and other gases contained in the molten metal by reaction of a reducing gas generated from a reducing gas forming agent. The invention also acts to free the metal from non-metallic inclusion by reducing deoxidizers such as ferrosilicon, and ferromanganese to metallic elements and by introducing said metallic elements into the ingot as an alloy to form metal having good qualities in elongation, reduction of area and bending resulting from said metallic elements.

In practice of the invention, it will be seen that between about 0.9 to about 10 Kg. of the reducing-gas forming hydrocarbon material, usually liquid, is used per 1000 Kg. of molten metal being treated. One part of such hydrocarbon is used together with from about 3 to about 5 parts by weight of a carbon or carbonaceous material.

' Some practical applications of the reforming process of the present invention will now be described in detail.

In one application of the invention to the manufacture of steel ingots of the JIS standard SMSOA by use ofa -ton basic electric arc furnace, the molten metal teemed therefrom was covered with a mixture ofliquid petroleum hydrocarbon with solid carbonaceous material first in the ladle and then in ingot molds. The ingots formed were ofimproved quality, having a composition including 0.17% C, 0.35% Si, 0.98% Mn and 0.018% P, and contained only limited amounts of gases including 0.005% oxygen and 0.000l% hydrogen in contrast to the conventional oxygen content of from 0.015 to 0.020% and hydrogen content of from 0.0005 to 0.0006%. For each melt of about 45 tons, 0.95 Kg/ton of kerosene and 4.7 Kg/ton of carbonaceous material were used in the ladle and casting molds by dipping the cover material in kerosene for impregnation. The cover material (carbonaceous material) used in ladle includes sheets of straw mat and one used in casting molds includes chaff and floatboards of wood.

It has been found from a composition of the ingot formed in contrast to that of a known or ordinary process that the ingot can be purified according to the present invention by reducing gases formed in the ingot Based on the temperature-specific heat relationships obtained by the adiabatic method, the heat requirements Q for heating from 600 C. to 850 C. were calculated as shown below, where process) namely oxygen and hydrogen gases to limited amounts. 5 O

In another example, the method of the present inven- =J C dt,

tion was applied to the manufacture of copper alloy ingots employing a ISO-kg crucible. High quality ingots of a copPer'mamum alloy mcludhng 968% Cu and Cp representing specific heat of the steel and d1, the 3.18% T1 were produced employing floatboards as 1 temperature differential cover material in both ladle and ingot mold. Two sets of 3.0 kg. each of boards were dipped in advance in kerosene and thus impregnated with approximately 500 grams and 100 grams of kerosene for use in the Type of Steel Q Cal/gr after h Q- CuUsr hcfmc h ll'lVCnllVe PI'OCCSS lnVCntlVC pfUCCbb The novel copper-titanium alloy ingot and conven- $541 43.4 00.2 tional one, both having a height of more than 40 cm 555C and a cross section of about 4 cm X 4 cm, were tested gwmg the followmg results Because of the special thermal characteristics described above, ingots of materials: reformed by the inventive process have noticeable merits as forging mate- Comparison Between Conventional and rial, requiring only one-half ofthe number of heats con- C........tzzrtgzt 'aaa asters. vemionally reqwed m fergmg e P m from the case of common steel ingots their core portlons can hardly be heated satisfactorily even if the ingots are exg f t Center Cm Center g ternally heated to such an extent that their surfaces are burnt or mflamed, the ingots formed according to the 3945 3920 invention can readily be heated with substantial uni- 39 O 3 08 3 18 formity and thus do not involve any danger ofoverhcat- 3.14 3.02 39.5 16 i i ing or causing the material at corners to flow under ex- 39 0 3 00 3 l6 cessive heat. Also, they can be forged or rolled with efficiency even at lower temperatures of the order of 'Hs indicates the Shore hardness measured in the core region of the lngot from 700 to 800 In a further application of the present invention, mol- Ffom Said table, it has been found that the Shore ten iron from acupola was reformed by use ofa 1:3 oilhafdness 35 Well as the titanium Content in the carbon mixture in the ladle bottom. The carbon matehovel Copper-titanium alloy ingots of the invention rial, breeze or graphite, was used in the form of being have been uniform throughout the ihgotsencapsulated in open-ended iron tubes. Use of about From this table and m mic gr phi comparison 10 Kg. of reducing-gas forming materials for each melt made between the inventive and conventional ingots, it 40 f 1,000 k v satisfactory r sults, the aterial thus has been found that alloy ingots of the desired composireformed being found particularly suitable for use as tion can be obtained according to the present invention at i l f rolls, in t cases and other high grade iron which include no segregation and have finer crystal ti s, grains than those obtainable by the conventional pro- Substantially the sa e oil-carbon mixture was also cess. Previously, it has been usual that titanium in the f d ff ti t r f ordinary lte ste l as melt and particularly in itS surface region comes in teemed from an electric or open-hearth furnace or a contact with the external air to form titanium oxide and converter, In these cases, the reforming mixture was as such tends to escape. used in the bottom of the ladle.

In production Of Steel ingots 0f 53 a 555C As for steel making pig iron, it has been found that specimens sized 20 mm X 15 mm d were prepared acit can be supplied according to the present invention at cording to same method as that Of Steel got Of 1 a price of less than twothirds of the current market SMSOA for analysing composition of the steel prori f charcoal pig iron. duced and evaluation of their specific heats, respec- Some data of iron and steel production performed tively. according to the present invention are shown below in The compositions of these steels, reformed and not 55 comparison with data obtained from the conventional reformed, were determined as follows: process.

Type of Steel Composition C Si Mn P S Cu Sn 5541 (before 0.13 0.19 0.54 0.025 0.010 0.10 0.020

process) (after 0.17 0.22 0.45 0.024 0.019 0.09 0.022

process) 855C (before 0.50 0.27 0.71 0.029 0.020 0.12

process) (after 0.55 0.25 0.64 0.023 0.018 0.08 a

EXAMPLE 1 Mechanical Properties of Products Bending 3-ton ingots of JIS SM50A steel were produced by Charge i e d 'f q t use of a 10-ton electr1c furnace addmg 55 Kg of charg f gf r a 8 33? coal and 11 Kg of kerosene as a reducing gas formtng men. material in the ladle only for 11,604 Kg charge. tive) Al 9 28.5 42.9 24.0 0 A2 12 28.3 44.3 26.0 0 Charge Materials used, in Kg. A3 0 Item Charge No. (cpnvem Scrap a i 9 24 0 43 5 3 x (Inventive) (Convent1onal) 10 B2 12 X 3 3 No. 1 heavy 4,1300 3.200 B3 X Fresh-cut pressed 6,500 7,800 230 220 O Sattsfactory Fe-Si '25 X Ca-Si 30 Fe-Al 4 3 5 Tot l 11,604 11,278

3 EXAMPLE 3 Effects of the Inventive Process upon Cast Iron Before Process Process Chemical C Si Mn P S C Si Mn P S Composition.% 3.82 L66 0.44 0.09 0.062 3.74 1.66 0.44 0.09 0.062 Shore hardness 35 31 Additives None For 400 Kg melt. 20 Kg chaff and 4 Kg (5 liters) kerosene were used in ladle Features of Ordinary Improved fluidity, Molten state melt maintained longer Blowholes Some None Segregation Some None Depth of4n 3 mm 12 mm probing The chemical composition and some mechanical properties of the product as shown below:

Chemical composition of products, in C Si Some examples of application of the present invention to the making of nonferrous metal castings will Charge No. Mn P S A 0.16 0.23 1.30 0.022 0.016 (Inventive) B 0.17 0.26 1.32 0.033 0.012 (Conventional) Mechanical properties of products Charge Direction Thickness Yield Tensile Elonga- Bending test of of rolled point strength tion, No. specimen plate,mm kg/mm kg/mm 1.5t 0.t A TC 22 32.4 55.8 26.5 0 0 (inventive) TL do. 32.9 do. 27.0 0 0 BC do. 33.0 56.5 25.5 0 0 BL do. 32.6 do. 26.5 o 0 B TC 22 unknown 56.6 21.5 0 X (conventional) TL do. do. 56.2 24.5 0 X BC do. 42.8 56.1 21.5 o x BL do. unknown 56.8 24.5 0 A TC Top crosswise TL Top lengthwise BC Bottom crosswise BL Bottom lengthwise 1.5'180" hending. folded 33-mtn radius 0 130 bending, closely folded O Satisfactory X No good A Surface cracks formed 1 EXAMPLE 2 next be described. In these examples, satisfactory re- Rimmed steel was produced in the ingot Size f 3 suits were obtained by use of an oil-carbon mixture, tons, from substantially the same furnace charge and Yvhlch Included kerosene charfioal and/0r P additives as used in Example 1. The chemical composii an approprlate ratlo Q Included kerosene tion and some mechanical properties of the produce lmpregnated cardboard or mlllboard- Also, u a steel f llo t1ally the same results were obtamed by sprmkllng kerosene-impregnated chaff over the molten metal Chemical composition products, in while it is being tapped. It was also found effective to Charge Mn P S sprinkle kerosene-impregnated charcoal dust over the 1 molten metal at times re uired. (Inventive) A1 0.15 0.43 0.018 0.027 First, in the making of pure copper castings, 0.44 Kg 2; 5 3 5-1 g-gg 33%;? 0.55 liter) of kerosene and 2.2 Kg ofchaff were added (Conventional) to each 40-Kg melt of pure copper. This was efg; 35 I 8:; 8-8;? 8%; fective to substantially improve the fluidity of the melt B3 0.14 0.43 do. 0.027 and to enable it to maintain its molten state for a subcluded no air voids nor blowholes, exhibiting a finer columnar crystal structure than those conventionally obtained.

Secondly, white-metal castings of the composition including approximately 74% Pb, 14% Sb and the rest of 12% Sn were formed by the inventive and conventional processes. The type and amount of the reforming mixture used in the inventive process and its effect upon the casting characteristics and mechanical properties of the melt and castings therefrom were substantially the same as described above in connection with pure copper castings.

After all, in casting either ferrous or nonferrous metals, the process of the present invention can be used to advantage as it eliminates undesirable orientation and segregation otherwise occurring in the metal cast, enables continuous casting operation, and helps, to give products which can be rolled with extreme uniformity and are highly gas-tight, corrosion-resistant and less fatiguing.

The advantageous features of different reformed casting materials or cast products obtainable to the present invention can be summarized as follows:

1. Even with relatively high P and S contents, the reformed materials or products are generally comparable in quality with corresponding conventional materials or products of lower P and S contents.

2. Castings formed according to the present invention are also comparable to corresponding conventioanlly vacuum-cast products in physical qualities. This fact suggests the importance of the hydrogen gas content of the molten metal.

3. Even steel castings as cast can be machined with satisfactory efficiency.

4. No shrinkage holes are formed in the core region of castings.

5. Steel highly excellent as material for Japanese swords can be prepared by the process of the invention.

6. Good hardenability and no quenching cracks.

7. Good weldability.

8. Higher weather resistance.

In addition, the use of oil as a mixture component is intended to promote the gasfication of carbon in the mixture. This is necessary to preclude increase in carbon content of the metal and any storage of oil used which may cause carburizing.

It is to be clearly understood that the formation of reducing gases in the molten metal effected according to the present invention is an exothermal reaction, serving to expel most of harmful gases out of the metal just as in vacuum degasification.

The carbon or carbonaceous material used is usually selected from the group of materials comprising charcoal, coke electrode chips, graphite, chaff, straw, pasteboards, dry fiber, cardboards, mill boards, and float boards of wood.

Though the process of the present invention can be performed, as described hereinbefore, solely in the ladle or in casting molds or in the chute arranged to direct tapped molten metal to the ladle, the merits of the inventive reforming procedure can be further enhanced by applying it to a plurality of consecutive casting stages typically associated with a transfer ladle and casting molds and/or by applying the reforming mixture to both top and bottom regions of the molten metal in the ladle or in molds or in both. Recommendable cover materials other than those named hereinbefore include 10 ordinary organic cover or heat-insulating materials for hot-top use, such as 'waste straw rope, saw dust, straw ashes and wood ashes. The hydrocarbon materials usable with these and other cover materials need not belimited to any particular kind but heavy petroleum oil, kerosene, grease or the like are readily available and are relatively cheap materials so that their use is recommended. Among others, grease is preferable as it forms sustaining flames. But, animal oil, vegetable oil, fats, benzene and wax may also be used.

Use of reducing deoxidizers is facilitated by the present invention as substances such as ferrosilicon and ferrormanganese are reduced to elemental form and alloy with the metal being formed into an ingot as alloying materials to improve the properties thereof.

In adding the materials to the molten metal, the materials may be sprayed, thrown, dropped, deposited, or

be otherwise applied or added to the metal.

Very desirable results are obtained from practice of the invention and metals with improved properties are.

obtained. I

While several complete embodiments of the invention have been disclosed herein, it will be appreciated that modification of these particular embodiments of the invention may be resorted to without departing from the scope of the invention as defined in the appended claims.

What is claimed is:

1..A metaltreating process wherein molten ferrousmetal is being processed, and comprising the step of adding to the molten metal from about 0.9 to about 10 Kg. of a hydrocarbon material which will form a reducing gas and a correlated amount of carbon containing material for each 1,000 Kg of molten metal present and wherein approximately one part by weight of hydrocarbon material selected from the group consisting of animal, vegetable and petroleum oils, kerosene, benzene,

wax and greases is used with approximately three to five parts by weight ofa carbon-containing material se lected from the group consisting of charcoal, coke, electrode chips, graphite, chaff, pasteboards and floatb oards.

2. A metal treating process as in claim 1 and comprising adding the materials to the molten metal in the ladle.

3. A metal treating process as in claim 1 and comprising adding the materials to the molten metal as it is flowing into the ladle.

4. A metal treating process as in claim 2 and comprising adding the materials to the molten metal by placing the materials in the bottom of the ladle before the molten metal is deposited in the ladle.

5. A metal treating process as in claim land compris ing adding the materials to the molten metal by placing the materials in the bottom ofthe mold before the mo]- ten metal is poured therein.

6. A metal treating process as in claim 1 where a portion ofeach of the materials is deposited onto the molten metal in the ladle and the remaining quantities of the materials are brought into contact with the molten metal in the mold.

7. A metal treating process as in claim 1 including spreading the carbon-containing material over the surface of the molten metal, and spraying the hydrocarbon material onto the carbon-containing material and molten metal.

8. A metal treating process as in claim 1 where the materials are immersed in the molten metal.

9. A metal treating process as in claim 1 including the step of impregnating the carbon containing material with the hydrocarbon material prior to adding such materials to the molten metal.

10. A non-ferrous metal treating process wherein a molten metal is being processed and comprising the step of effecting contact of from about 0.9 to about Kg of a reducing gas forming agent and a predetermined amount of carbon containing material for each 1,000 Kg of molten metal present with the molten metal, and wherein approximately one part by weight of a hydrocarbon material is said agent and is selected from the group consisting of animal, vegetable and petroleum oils, kerosene, benzene, wax and greases is used with approximately three to five parts by weight of a carbon-containing material selected from the group consisting of charcoal, coke, electrode chips, graphite, chaff, and other organic cover materials.

11. A metal treating process as in claim 10 and comprising bringing the materials into contact with the molten metal in the ladle.

12. A metal treating process as in claim 10 and comprising contacting the materials and molten metal in the mold.

13. A metal treating process as in claim 10 comprising contacting a portion of each of the materials with the molten metal in the ladle and the remaining quantities of the materials are brought into contact with the molten metal in the mold.

14. In a metal casting process, a method of reforming molten metal to be cast comprising the step of placing a mixture of a carbon containing material and a hydrocarbon, in a ratio ranging between about 3 to l and about 5 to 1 parts by weight in direct contact with the molten metal for vigorous reducing-gas forming reaction therewith while the molten metal is being tapped from a melting vessel into a ladle, said hydrocarbon being employed in an amount ranging between about 0.9 kilogram and about 10 kilograms per 1000 kilograms of the molten metal.

15. In a metal casting process as in claim 14 where said carbon containing material is amorphous carbon.

16. A method as claimed in claim 15 in which said mixture is placed in the bottom of the ladle before the molten metal is run therein from the melting vessel.

17. A method as claimed in claim 15 in which said mixture is thrown into the ladle concurrently with the molten metal when the latter is run into the ladle from the melting vessel.

18. A non-ferrous metal treating process as in claim 10 including spreading the carbon containing material over the surface of the molten metal and spraying the hydrocarbon material onto the carbon-containing material and molten metal.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 837 Dated Kafniaru 28, 1975 Inventor(s) Kokichi Otani It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Line 49, Column 10, line 1 of Claim 4, change "2" to 1 Signed and sealed this 13th day of May 1975.

(SEAL) Attest':

C MARSHALL DANN RUTH C. MASON Commissioner of Patents Attesting Officer and Trademarks ORM PO-1050 (10-69) USCOMM-Dc go ng- 59 w: u s. GOVERNMENT PRINTING OFFICE 19" o-ase-ssa, 

2. A metal treating process as in claim 1 and comprising adding the materials to the molten metal in the ladle.
 3. A metal treating process as in claim 1 and comprising adding the materials to the molten metal as it is flowing into the ladle.
 4. A metal treating process as in claim 2 and comprising adding the materials to the molten metal by placing the materials in the bottom of the ladle before the mOlten metal is deposited in the ladle.
 5. A metal treating process as in claim 1 and comprising adding the materials to the molten metal by placing the materials in the bottom of the mold before the molten metal is poured therein.
 6. A metal treating process as in claim 1 where a portion of each of the materials is deposited onto the molten metal in the ladle and the remaining quantities of the materials are brought into contact with the molten metal in the mold.
 7. A metal treating process as in claim 1 including spreading the carbon-containing material over the surface of the molten metal, and spraying the hydrocarbon material onto the carbon-containing material and molten metal.
 8. A metal treating process as in claim 1 where the materials are immersed in the molten metal.
 9. A metal treating process as in claim 1 including the step of impregnating the carbon containing material with the hydrocarbon material prior to adding such materials to the molten metal.
 10. A non-ferrous metal treating process wherein a molten metal is being processed and comprising the step of effecting contact of from about 0.9 to about 10 Kg of a reducing gas forming agent and a predetermined amount of carbon containing material for each 1,000 Kg of molten metal present with the molten metal, and wherein approximately one part by weight of a hydrocarbon material is said agent and is selected from the group consisting of animal, vegetable and petroleum oils, kerosene, benzene, wax and greases is used with approximately three to five parts by weight of a carbon-containing material selected from the group consisting of charcoal, coke, electrode chips, graphite, chaff, and other organic cover materials.
 11. A metal treating process as in claim 10 and comprising bringing the materials into contact with the molten metal in the ladle.
 12. A metal treating process as in claim 10 and comprising contacting the materials and molten metal in the mold.
 13. A metal treating process as in claim 10 comprising contacting a portion of each of the materials with the molten metal in the ladle and the remaining quantities of the materials are brought into contact with the molten metal in the mold.
 14. In a metal casting process, a method of reforming molten metal to be cast comprising the step of placing a mixture of a carbon containing material and a hydrocarbon, in a ratio ranging between about 3 to 1 and about 5 to 1 parts by weight in direct contact with the molten metal for vigorous reducing-gas forming reaction therewith while the molten metal is being tapped from a melting vessel into a ladle, said hydrocarbon being employed in an amount ranging between about 0.9 kilogram and about 10 kilograms per 1000 kilograms of the molten metal.
 15. In a metal casting process as in claim 14 where said carbon containing material is amorphous carbon.
 16. A method as claimed in claim 15 in which said mixture is placed in the bottom of the ladle before the molten metal is run therein from the melting vessel.
 17. A method as claimed in claim 15 in which said mixture is thrown into the ladle concurrently with the molten metal when the latter is run into the ladle from the melting vessel.
 18. A non-ferrous metal treating process as in claim 10 including spreading the carbon containing material over the surface of the molten metal and spraying the hydrocarbon material onto the carbon-containing material and molten metal. 